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Adsorption
Due to unbalanced attraction forces, accumulation of molecular species at the surface rather
than in the bulk of a solid or liquid is termed as adsorption. The molecular species accumulates
at the surface is termed as adsorbate and the material on the surface of which the adsorption
takes place is called adsorbent, e.g..
(i) O2, H2, C12, NB3 gases are adsorbed on the surface of charcoal.
(ii) Silica gels adsorb water molecules from air.
Charcoal, silica gel, metals such as Ni, Cu, Ag, Pt and colloids are some adsorbents.
ΔG= ΔH – TΔS,
For the negative value of ΔG,in a system, in which randomness decreases, ΔH must be
negative. Hence, adsorption is always exothermic.
Desorption
Sorption
It is a process in which both adsorption and absorption take place simultaneously, the term
sorption is simply used.
When the concentration of the adsorbate is more on the surface of the adsorbent than in the
bulk, it is called positive adsorption.
On the other hand, if the concentration of the adsorbate is less relative to its concentration in
the bulk, it is called negative adsorption, e.g., when a dilute solution of KCl is shaken with
blood charcoal, it shows negative adsorption.
(a) Nature of adsorbent Same gas may be adsorbed to different extents on different adsorbent.
(b) Surface area of the adsorbent Greater the surface area, greater is the extent of adsorption.
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(c) Nature of the gas being adsorbed Greater is the critical temperature of a gas, greater are
the van der Waals’ forces of attraction and thus, greater is the adsorption.
Applying Le-Chatelier principle, increase of temperature decreases the adsorption and vice-
versa.
(e) Pressure Adsorption increases with pressure at constant temperature. The effect is large if
temperature is kept constant at low value.
(f) Activation of the solid adsorbent Activation means increasing the adsorbing power of the
solid adsorbent. This can be done by subdividing the solid adsorbent or by removing the gases
already adsorbed by passing superheated steam.
Adsorption Isotherms
It is the plot of the mass of gas adsorbed per gram of adsorbent (x / m) versus equilibrium
pressure at constant temperature.
It gave an empirical relationship between the quantity of gas adsorbed by unit mass of solid
adsorbent and pressure at a particular temperature. It can be expressed by the equation.
x / m = kp1/n …(i)
Where, x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p, k and n are
constants which depend on the nature of the adsorbent and the gas at a particular temperature.
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x / m = kC1/n
where, C is the equilibrium concentration. On taking logarithm of the above equation, we have
According to Langmuir, the degree of adsorption is directly ProPOrtional to e, i.e., the fraction
of surface area occupied.
x / m α θ = kθ
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Adsorption Isobars
These are plots of x / m us temperature t at constant pressure. For physical and chemical
adsorption, they are shown below.
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Adsorption Isostere
These are the plot of temperature versus pressure for a given amount of adsorption
Applications of Adsorption
Catalysis
Catalyst is a chemical substance which can change the rate of reaction without being used up in
that reaction and this process is known as catalysis
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A catalyst may be positive (i.e., increases rate of reaction) or negative (i.e., decreases rate of
reaction).
Types of Catalysis
(a) Homogeneous catalysis In this catalysis, and the catalyst reactants are in the same physical
state [phase], e.g.,
(c) Autocatalysis When one of the product of a reaction acts as catalyst, the process is called
autocatalysis.
Characteristics of Catalysts
Promoters are chemical substances that enhance the activity of a catalyst while poisons
decreases the activity of a catalyst
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(i) Activity The activity of a catalyst depends upon the strength of chemisorption to a large
extent. The adsorption should be reasonably strong but not so strong that they become
immobile and no space is available for other reactants to get adsorbed.
(ii) Selectivity The selectivity of a catalyst is its ability to direct a reaction to yield a particular
product, e.g., starting with Hz and CO using different catalysts, we get different products.
Shape–selective catalysis The catalytic reaction that depends upon the pore structure of the
catalyst and the size of the reactant and product molecules is called shape-selective catalysiS.
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An important zeolite catalyst used in the petroleum industry is ZSM-S.lt converts alcohols
directly into gasoline.
Enzyme Catalysis
Enzymes are complex nitrogenous organic compounds which are Produced by living plants and
animals. They are actually protein molecules of high molecular mass and form colloidal
solutions in water.
(Source of invertase, zymase and maltose is yeast and that of diastase is malt. Soybean is the
source of urease.)
(v) In stomach, the pepsin enzyme converts proteins into peptides while in intestine, the
pancreatic trypsin converts proteins into amino acids by hydrolysis.
High efficiency One molecule of an enzyme may transform one million molecule of
reactant per minute.
Highly specific nature Each enzyme catalyst cannot catalyse more than one reaction.
Optimum temperature Enzyme catalyst gives higher yield at optimum temperature i.e.,
at 298-310 K. Human body temperature, i.e., at being 310 K is suited for enzyme
catalysed reactions.
Optimum pH The rate of an enzyme catalysed reaction is maximum at optimum pH
range 5 to 7.
Activators Activators like ions such as Na+ ,Ca 2+, Mn2+ help in the activation of
enzymes which cannot act on their own strength.
Co-enzyme Co-enzymes are the substance having nature similar to the enzyme and their
presence increases the enzyme activity. Mostly vitamins act as co-enzymes.
Effect of Inhibitors Inhibitors slow down the rate of enzymatic reaction. The use of
many drugs is based on enzyme inhibition action of those drugs in the body